Adsorption heat pump and use of adsorbent as adsorbent for adsoprtion heat pump

ABSTRACT

An adsorption heat pump is provided in which water vapor can be efficiently adsorbed and desorbed using a heat source having a lower temperature than ones heretofore in use because the pump employs an adsorbent which has a large difference in water adsorption amount in adsorption/desorption and can be regenerated (release the adsorbate) at a low temperature.  
     The invention provides an adsorption heat pump which comprises an adsorbate, an adsorption/desorption part having an adsorbent for adsorbate adsorption/desorption, a vaporization part for adsorbate vaporization which has been connected to the adsorption/desorption part, and a condensation part for adsorbate condensation which has been connected to the adsorption/desorption part, wherein the adsorbent, when examined at 25° C., gives a water vapor adsorption isotherm which, in the relative vapor pressure range of from 0.05 to 0.30, has a relative vapor pressure region in which a change in relative vapor pressure of 0.15 results in a change in water adsorption amount of 0.18 g/g or larger.

TECHNICAL FIELD

[0001] The present invention relates to an adsorption heat pumpemploying a specific adsorbent and use of the specific adsorbent as anadsorbent for an adsorption heat pump.

BACKGROUND ART

[0002] In an adsorption heat pump, the adsorbent having an adsorbate,e.g., water, adsorbed thereon is heated to desorb the adsorbate in orderto regenerate the adsorbent, and the adsorbent dried is cooled to atemperature to be used for adsorbate adsorption before being used foradsorbate adsorption again.

[0003] Absorption type heat pumps in which waste heat or heat having arelatively high temperature (120° C. or higher) is utilized as a heatsource for adsorbent regeneration have already come into practical use.However, since the heat obtained from cogeneration apparatus, fuelcells, cooling water for automotive engines, solar energy, or the likegenerally has a relatively low temperature of 100° C. or below, itcannot be utilized as a heat source for driving the absorption type heatpumps presently in practical use. It has been desired to effectivelyutilize low-temperature waste heat of 100° C. or lower, especially from60° C. to 80° C. In particular, there is a strong desire for thepractical use thereof in motor vehicles which generate waste heat inlarge quantities.

[0004] In adsorption heat pumps, the adsorption properties required ofadsorbents vary considerably depending on the temperatures of utilizableheat sources even though the heat pumps operate on the same principle.For example, the temperatures of higher-temperature-side heat sourcesare from 60° C. to 80° C. in the case of waste heat from gas enginecogeneration and from solid polymer type fuel cells and are from 85° C.to 90° C. in the case of cooling water for automotive engines. Thetemperatures of cooling-side heat sources also vary depending on theplaces where the apparatus is installed. For example, the cooling-sideheat source temperatures in the case of motor vehicles are temperaturesobtained with the radiators, while those in buildings, houses, and thelike are the temperatures of water-cooling towers, river water, etc.Namely, the operating temperatures for an adsorption heat pump are asfollows. In the case of installation in buildings or the like, thelower-side temperatures are from 25° C. to 35° C. and the higher-sidetemperatures are from 60° C. to 80° C. In the case of installation inmotor vehicles or the like, the lower-side temperatures are about from30° C. to 45° C. and the higher-side temperatures are about from 85° C.to 90° C. There is hence a desire for an apparatus capable of beingoperated even with a small temperature difference between thelower-temperature-side heat source and the higher-temperature-side heatsource so as to effectively utilize waste heat. An adsorbent to beapplied to such apparatus is also desired.

[0005] Typical adsorbents known as adsorbents for adsorption heat pumpsare zeolite 13X and A-form silica gel.

[0006] Recently, zeolites are being investigated, such as a mesoporousmolecular sieve (e.g., FSM-10) synthesized using the micellar structureof a surfactant as a template (Japanese Patent Laid-Open No.178292/1997) and a porous aluminum phosphate molecular sieve for use asa desiccant material commonly referred to as AlPO₄ (Japanese PatentLaid-Open No. 197439/1999).

[0007] It has already been reported that the temperature dependence ofadsorption properties is important for the adsorbents for adsorptionheat pumps (Kagaku Kôgaku Ronbunshû, Vol. 19, No.6 (1993),pp.1165-1170). There is a report therein that SG3 (manufactured by FujiSilysia Ltd.) shows a large temperature dependence and SG1 (manufacturedby the same) does not.

[0008] Furthermore, it has been reported that the adsorption performanceof AlPO₄-5, which is a porous aluminum phosphate molecular sieve,depends on temperature. Specifically, the adsorption performance at 25°C. and that at 30° C. are shown (Colloid Polym Sci, 277 (1999)pp.83-88). Likewise, the temperature dependence of AlPO₄-5 has beenreported; adsorption isotherms obtained in an adsorption process at 20°C., 25° C., 30° C., 35° C., and 40° C. are shown (Dai-16-kai ZeoraitoKenkyû Happyô Kai Kôen Yokô-shû, p.91; Nov. 21 and 22, 2000).

[0009] Use of various adsorbents in adsorption heat pumps is beinginvestigated. However, our investigations revealed that there is yetroom for improvement in adsorption performance so as to enableapplication to an apparatus capable of being operated even with a smalltemperature difference between the lower-temperature-side heat sourceand the higher-temperature-side heat source.

DISCLOSURE OF THE INVENTION

[0010] In order for an apparatus to sufficiently operate even when theatmosphere surrounding the adsorbent has relatively high temperatures,it is necessary to adsorb the adsorbate at a low relative vaporpressure. In order to reduce the size of an apparatus by reducing theamount of the adsorbent to be used, the amount of an adsorbate adsorbedonto and desorbed from the adsorbent should be large. Furthermore, inorder to utilize a low-temperature heat source for adsorbate desorption(adsorbent regeneration), it is necessary that the desorptiontemperature is low. Namely, it is important that an adsorbent for use inadsorption heat pumps is one which (1) adsorbs an adsorbate at a lowrelative vapor pressure (capable of high-temperature adsorption), (2)attains a large adsorption/desorption amount, and (3) is capable ofadsorbate desorption at a high relative vapor pressure (capable oflow-temperature desorption).

[0011] The invention has been achieved for the purpose of providing anefficient adsorption heat pump which employs an adsorbent capable ofadsorbate adsorption/desorption in a low-relative-vapor-pressure region.

[0012] Another object of the invention is to provide use of an adsorbentcapable of adsorbate adsorption/desorption in alow-relative-vapor-pressure region as an adsorbent for adsorption heatpumps.

[0013] Still another object of the invention is to provide an adsorptionheat pump having practically effective adsorption performance.

[0014] The invention provides, in one aspect thereof, an adsorption heatpump which comprises an adsorbate, an adsorption/desorption part havingan adsorbent for adsorbate adsorption/desorption, a vaporization partfor adsorbate vaporization which has been connected to theadsorption/desorption part, and a condensation part for adsorbatecondensation which has been connected to the adsorption/desorption part,wherein the adsorbent, when examined at 25° C., gives a water vaporadsorption isotherm which, in the relative vapor pressure range of from0.05 to 0.30, has a relative vapor pressure region in which a change inrelative vapor pressure of 0.15 results in a change in water adsorptionamount of 0.18 g/g or larger.

[0015] The invention further provides, in another aspect thereof, use ofthe adsorbent described above as an adsorbent for adsorption heat pumps.

[0016] In still another aspect thereof, the invention provides anadsorption heat pump which comprises an adsorbate, anadsorption/desorption part having an adsorbent for adsorbateadsorption/desorption, and a vaporization/condensation part foradsorbate vaporization/condensation which has been connected to theadsorption/desorption part, characterized in that the adsorbentcomprises a zeolite containing aluminum, phosphorus, and a heteroatom inthe framework structure.

[0017] In a further aspect thereof, the invention provides an adsorptionheat pump which comprises (a) an adsorbate, (b) an adsorption/desorptionpart having an adsorbent for adsorbate adsorption/desorption, (c) avaporization part for adsorbate vaporization which has been connected tothe adsorption/desorption part, and (d) a condensation part foradsorbate condensation which has been connected to theadsorption/desorption part, characterized in that the adsorbentcomprises a zeolite containing aluminum, phosphorus, and silicon in theframework structure, and that the zeolite gives a ²⁹Si-NMR spectrum inwhich the integrated intensity area for the signals at from −108 ppm to−123 ppm is not more than 10% based on the integrated intensity area forthe signals at from −70 ppm to −123 ppm.

[0018] Furthermore, the present inventors directed attention to the factthat in the adsorption/desorption parts of heat pumps, the operatingtemperature during adsorbate adsorption differs from that duringadsorbate desorption. The inventors made intensive investigations inview of the fact. As a result, they have found that a heat pump havingpractically useful adsorption performance is one employing an adsorbentin which the value of a specific difference in adsorption amountdetermined from (1) an adsorption isotherm obtained at anadsorption/desorption part temperature during adsorption operation and(2) a desorption isotherm obtained at an adsorption/desorption parttemperature during desorption operation is within a given range. Theinvention has been achieved based on this finding.

[0019] Namely, in still a further aspect thereof, the invention providesthe following.

[0020] An adsorption heat pump which comprises (a) an adsorbate, (b) anadsorption/desorption part having an adsorbent for adsorbateadsorption/desorption, (c) a vaporization part for adsorbatevaporization which has been connected to the adsorption/desorption part,and (d) a condensation part for adsorbate condensation which has beenconnected to the adsorption/desorption part, characterized in that

[0021] (1) the adsorbent comprises a zeolite containing at leastaluminum and phosphorus in the framework structure, and

[0022] (2) the adsorbent is a water vapor adsorbent having a region inwhich the adsorption amount difference as determined with the followingequation is 0.15 g/g or larger in the range in which the relative vaporpressure φ2 b during adsorption operation in the adsorption/desorptionpart is from 0.115 to 0.18 and the relative vapor pressure φ1 b duringdesorption operation in the adsorption/desorption part is from 0.1 to0.14:

Adsorption amount difference=Q 2−Q 1

[0023] wherein

[0024] Q1=adsorption amount at φ1 b as determined from a water vapordesorption isotherm obtained at a temperature (T3) used for desorptionoperation in the adsorption/desorption part

[0025] Q2=adsorption amount at φ2 b as determined from a water vaporadsorption isotherm obtained at a temperature (T4) used for adsorptionoperation in the adsorption/desorption part, provided that

[0026] φ1 b (relative vapor pressure during desorption operation in theadsorption/desorption part)=[equilibrium water vapor pressure at thetemperature of coolant (T2) cooling the condenser]/[equilibrium watervapor pressure at the temperature of heat medium (T1) heating theadsorption/desorption part]

[0027] φ2 b (relative vapor pressure during adsorption operation in theadsorption/desorption part)=[equilibrium vapor pressure at thetemperature of cold (T0) generated in the vaporizationpart]/[equilibrium vapor pressure at the temperature of coolant (T2)cooling the adsorption/desorption part]

[0028] (wherein T0=5 to 10° C., T1=T3=90° C., and T2=T4=40 to 45° C.)

BRIEF DESCRIPTION OF THE DRAWINGS

[0029]FIG. 1 is a diagrammatic view of an adsorption heat pump.

[0030]FIG. 2 is a water vapor adsorption isotherm (25° C.) for SAPO-34(manufactured by UOP LLC) in Example 1.

[0031]FIG. 3 is a ²⁹Si-MAS-NMR spectral chart for SAPO-34 (manufacturedby UOP LLC) in Example 1.

[0032]FIG. 4 is a water vapor adsorption isotherm (25° C.) for thezeolite of Example 2.

[0033]FIG. 5 is an Si-MAS-NMR spectral chart for the ²⁹zeolite ofExample 2.

[0034]FIG. 6 is a water vapor adsorption isotherm (25° C.) for thezeolite of Example 3.

[0035]FIG. 7 is water vapor adsorption isotherms for SAPO-34(manufactured by UOP LLC) in Example 4 which were obtained in adsorptionprocess at 40° C. and desorption process at 90° C.

[0036]FIG. 8 is water vapor adsorption isotherms for SAPO-34(manufactured by UOP LLC) in Example 4 which were obtained in adsorptionprocess at 45° C. and desorption process at 90° C.

[0037]FIG. 9 is a water vapor adsorption isotherm (25° C.) for thezeolite of Reference Example.

[0038]FIG. 10 is a ²⁹Si-MAS-NMR spectral chart for the zeolite ofReference Example.

[0039]FIG. 11 is a water vapor adsorption isotherm (25° C.) for A-formsilica gel in Comparative Example 2.

[0040]FIG. 12 is a water vapor adsorption isotherm (30° C.) for ALPO-5in Comparative Example 3.

[0041] In the figures, numeral 1 denotes an adsorption column, 2 anadsorption column, 3 an adsorbate piping, 4 a vaporizer, 5 a condenser,11 a heat medium piping, 111 a cooling-water inlet, 112 a cooling-wateroutlet, 113 a warm-water inlet, 114 a warm-water outlet, 115 a switchingvalve, 116 a switching valve, 21 a heat medium piping, 211 acooling-water inlet, 212 a cooling-water outlet, 213 a warm-water inlet,214 a warm-water outlet, 215 a switching valve, 216 a switching valve,30 an adsorbate piping, 31 a control valve, 32 a control valve, 33 acontrol valve, 34 a control valve, 300 an indoor unit, 301 a pump, 41 acold-water piping (inlet), 42 a cold-water piping (outlet), 51 acooling-water piping (inlet), and 52 a cooling-water piping (outlet).

BEST MODE FOR CARRYING OUT THE INVENTION

[0042] The invention will be explained below in more detail.

[0043] <Structure of Adsorption Pump>

[0044] First, the structure of adsorption heat pumps will be explainedusing the adsorption heat pump shown in FIG. 1 as an example.

[0045] An adsorption heat pump is constituted mainly of: an adsorbate;an adsorption/desorption part (adsorption columns 1 and 2) which ispacked with an adsorbent capable of adsorbate adsorption/desorption andserves to transfer the heat generated by adsorbate adsorption/desorptionto a heat medium (hereinafter the adsorption/desorption part issometimes referred to as adsorption columns); a vaporization part(vaporizer 4) which serves to take out the cold obtained by adsorbatevaporization; and a condensation part (condenser 5) which serves torelease outward the heat obtained by adsorbate condensation.

[0046] The vaporizer 4 contains a coolant (water in this embodiment) andis in a hermetically sealed state, with the inside being nearly vacuum.This vaporizer 4 is equipped inside with a heat exchanger 43 for heatexchange between the coolant and a heat medium (in this embodiment, afluid obtained by mixing water with an ethylene glycol-based antifreeze)which has undergone heat exchange in an indoor unit 300 with the airblowing into the room.

[0047] The adsorption columns 1 and 2 have, disposed therein, a heatexchanger having an adsorbent adhered to the surface thereof or packedtherein. The condenser 5 has, disposed therein, a heat exchanger 53 forcooling and condensing the vapor coolant (water vapor) released from theadsorption column 1 or 2 with a heat medium which has been cooled with,e.g., the outside air.

[0048] The adsorption columns 1 and 2, which are packed with anadsorbent, are connected to each other by an adsorbate piping 30. Thisadsorbate piping 30 has control valves 31 to 34 disposed therein. In theadsorbate piping, the adsorbate is present in the state of the vapor ofthe adsorbate or in the form of a mixture of the liquid and vapor of theadsorbate.

[0049] To the adsorbate piping 30 have been connected the vaporizer 4and the condenser 5. The adsorption columns 1 and 2 have been connectedin parallel arrangement to the vaporizer 4 and the condenser 5. Betweenthe condenser 5 and the vaporizer 4 is disposed a return piping 3 forreturning the adsorbate condensed by the condenser (preferablycondensate water resulting from regeneration) to the vaporizer 4.Numeral 41 denotes an inlet for cold water serving as a cooling outputfrom the vaporizer 4, and numeral 51 denotes a cooling-water inlet forintroducing cooling water into the condenser 5. Numerals 42 and 52denote a cold-water outlet and a cooling-water outlet, respectively. Thecold-water pipings 41 and 42 are connected to an indoor unit 300 forheat exchange with an indoor space (space to be air-conditioned) and toa pump 301 for circulating cold water.

[0050] A heat medium piping 11 and a heat medium piping 21 have beenconnected respectively to the adsorption column 1 and the adsorptioncolumn 2. The heat medium pipings 11 and 21 have switching valves 115and 116 and switching valves 215 and 216, respectively, disposedtherein. A heat medium serving as a heating source or cooling source forheating or cooling the adsorbent in the adsorption columns 1 and 2 iscaused to flow through the heat medium pipings 11 and 21, respectively.The heat medium is not particularly limited as long as it caneffectively heat/cool the adsorbent packed in the adsorption columns.

[0051] Warm water is introduced through an inlet 113 and/or inlet 213 byopening or closing switching valves (three-way valves) 115, 116, 215,and 216. The warm water introduced passes through the adsorption column1 and/or 2 and is then discharged through an outlet 114 and/or outlet214. Likewise, cooling water is introduced through an inlet 111 and/orinlet 211 by opening or closing the switching valves 115, 116, 215, and216, passes through the adsorption column 1 and/or 2, and is thendischarged through an outlet 112 and/or outlet 212.

[0052] The coolant piping which connects the vaporizer 4 to theadsorption columns 1 and 2 and the coolant piping which connects thecondenser 5 to the adsorption columns 1 and 2 have control valves 31 to34, which open or close the respective coolant pipings. These controlvalves 31 to 34, the pump 301 for heat medium circulation, and thethree-way valves 115, 116, 215, and 216 for controlling the flow of aheat medium are controlled by an electronic controller (not shown).

[0053] To the heat medium piping 11 and/or 21 have been connected anoutdoor unit disposed so as to be capable of heat exchange with theoutside air, a heat source which yields warm water, and a pump for heatmedium circulation (all of these are not shown). The heat source is notparticularly limited, and examples thereof include cogenerationapparatus, such as automotive engines, gas engines, and gas turbines,and fuel cells. In the case of automotive use, preferred examples of theheat source include automotive engines and automotive fuel cells.

[0054] <Outline of Adsorption Heat Pump Operation>

[0055] The operation of the air conditioning system (adsorption heatpump) according to this embodiment will be outlined below. The pump 301is operated to circulate the heat medium through the indoor unit 300 andthe vaporizer 4 to thereby vaporize the liquid coolant (preferablywater) in the vaporizer 4. The heat medium is thus cooled to cool theair to be blown into the room. Simultaneously with this operation, thecontrol valves 31 to 34 and the three-way valves 115, 116, 215, and 216are switched so that either of the two adsorption columns 1 and 2 is inthe adsorption mode and the other adsorption column is in the desorptionmode (regeneration mode).

[0056] Specifically, in the case where the first adsorption column 1 isto be operated in the adsorption mode and the second adsorption column 2is to be operated in the desorption mode, valve switching is conductedin the following manner. The three-way valve 115 and the three-way valve116 are regulated so as to establish connection to the cooling-waterinlet 111 side and the cooling-water outlet 112 side, respectively,while keeping the control valve 31 open and the control valve 33 close.Simultaneously therewith, the three-way valve 215 and the three-wayvalve 216 are regulated so as to establish connection to the warm-waterinlet 213 side and the warm-water outlet 214 side, respectively, whilekeeping the control valve 32 close and the control valve 34 open.

[0057] As a result, the coolant (water vapor) vaporized in the vaporizer4 flows into the first adsorption column 1 and is adsorbed onto theadsorbent packed therein. During this adsorption, the temperature ofthis adsorbent is kept at around the temperature of the surrounding airwith the cooling water introduced through the inlet 111.

[0058] On the other hand, warm water heated by a heat source (or thedriving engine in the case of application to a vehicle) is supplied tothe second adsorption column 2 through the warm-water inlet 213. As aresult, the adsorbent in the second adsorption column releases thecoolant which was adsorbed thereon in the adsorption mode. The coolant(water vapor) thus desorbed is cooled and condensed in the condenser 5for regeneration.

[0059] After the lapse of a given time period, the control valves 31 to34 and the three-way valves 115, 116, 215, and 216 are switched, wherebythe modes of the first adsorption column 1 and second adsorption column2 can be shifted to the desorption mode and the adsorption mode,respectively. By repeating such switching at a given interval, acontinuous cooling operation can be conducted.

[0060] <Adsorbents>

[0061] One feature of the invention resides in the adsorbents used inthe adsorption heat pumps.

[0062] <Adsorbent 1>

[0063] An adsorbent in the invention is an adsorbent which, whenexamined at 25° C., gives a water vapor adsorption isotherm which, inthe relative vapor pressure range of from 0.05 to 0.30, has a relativevapor pressure region in which a change in relative vapor pressure of0.15 results in a change in water adsorption amount of 0.18 g/g orlarger, preferably 0.2 g/g or larger. This adsorbent preferably is onein which that change in water adsorption amount in the range of from0.05 to 0.20 is 0.18 g/g or larger, preferably 0.2 g/g or larger.

[0064] Adsorbates are adsorbed as vapors onto adsorbents. A preferredadsorbent is a material which undergoes a large change in adsorbateadsorption amount in a narrow relative vapor pressure range. The reasonsfor this are as follows. When such an adsorbent undergoing a largechange in adsorption amount in a narrow relative vapor pressure range isused, the amount of the adsorbent necessary for obtaining the sameadsorption amount under the same conditions can be reduced and theadsorption heat pump can be operated even with a smaller temperaturedifference between the heat source for cooling and the heat source forheating.

[0065] The preference for that property of an adsorbent will becomeapparent from the following investigation.

[0066] First, the operating vapor pressure range for an adsorption heatpump is determined by the desorption-side relative vapor pressure (φ1 a)and the adsorption-side relative vapor pressure (φ2 a). The values of φ1and φ2 can be calculated using the following equations. The range offrom φ1 a to φ2 a is the relative vapor pressure range in which the pumpcan be operated.

Desorption-side relative vapor pressure (φ1 a)=[equilibrium vaporpressure (Tlow1)]/[equilibrium vapor pressure (Thigh)]

Adsorption-side relative vapor pressure (φ2 a)=[equilibrium vaporpressure (Tcool)/[equilibrium vapor pressure (Tlow2)]

[0067] The symbols have the following meanings.

[0068] Thigh (temperature of high-temperature heat source): Temperatureof heat medium used for desorbing adsorbate from adsorbent and therebyregenerating the adsorbent

[0069] Tlow1 (temperature of low-temperature heat source): Temperatureof adsorbate in condensation part

[0070] Tlow2 (temperature of low-temperature heat source): Temperatureof heat medium used for cooling regenerated adsorbent in preparation foradsorption

[0071] Tcool (temperature of cold generated): Temperature of adsorbatein the vaporization part, i.e., temperature of cold generated

[0072] The equilibrium vapor pressure can be determined from temperatureusing an equilibrium vapor pressure curve for the adsorbent.

[0073] Examples of the operating vapor pressure range in the case wherethe adsorbate is water are shown below. When the high-temperature heatsource temperature is 80° C. and the low-temperature heat sourcetemperature is 30° C., then the operating vapor pressure range (φ1 a-φ2a) is from 0.09 to 0.29. Likewise, when the high-temperature heat sourcetemperature is 60° C. and the low-temperature heat source temperature is30° C., then the operating relative water vapor pressure range (φ1 a-φ2a) is from 0.21 to 0.29. Furthermore, in the case where waste heat froman automotive engine is utilized for operating an adsorption heat pump,the high-temperature heat source temperature and the low-temperatureheat source temperature are estimated at about 90° C. and 30° C.,respectively, from a statement given in Japanese Patent Laid-Open No.2000-140625. In this case, the operating relative vapor pressure range(φ1 a-φ2 a) is from 0.06 to 0.29.

[0074] It can hence be thought that in the case where waste heat fromgas engine cogeneration or from a solid polymer type fuel cell orautomotive engine is utilized for operating an adsorption heat pump, theoperating relative vapor pressure range (φ1 a-φ2 a) is from 0.05 to0.30, preferably from 0.06 to 0.29. Namely, a material undergoing alarge change in adsorption amount in this operating moisture range ispreferred. Consequently, it is preferred to use a material which changesconsiderably in adsorption amount in the relative vapor pressure rangeof usually from 0.05 to 0.30, preferably from 0.06 to 0.29.

[0075] For example, the case where a cooling power of 3.0 kW (=10,800kJ/hr) is to be obtained with an adsorption heat pump is supposed. Thisvalue of 3.0 kW is the cooling ability of air conditions for use ingeneral motor vehicles. It is thought from investigations on the enginerooms of various motor vehicles that the volume of an adsorption heatpump is desirably up to 15 liter.

[0076] <<Adsorption Amount Difference>>

[0077] The weight of an adsorbent capable of being packed into a volumeof 15 liter or smaller is then determined.

[0078] The parts which should be mounted in the engine room includeadsorption column main bodies, a vaporizer, a condenser, and controlvalves. It is necessary that these parts are mostly united into anassembly having a volume of 15 liter or smaller. It is thought from ourinvestigations that the vaporizer, condenser, and valves can be arrangedin a space volume of 4.5 liter. Consequently, the volume of theadsorption column main bodies is about 10.5 liter or smaller. Since thepercentage packing of adsorbents in adsorption columns and the bulkdensity of adsorbents are usually about 30% and about 0.6 kg/liter,respectively, the weight of an adsorbent which can be packed (W) isabout 10.5×30%×0.6=1.89 kg.

[0079] Properties required of adsorbents will be explained next.

[0080] The cooling power R of an adsorption heat pump is expressed bythe following equation A.

R=(W·ΔQ·η _(c) ·ΔH/τ)·η_(h)  (equation A)

[0081] In equation A, W represents the weight of the adsorbent packedinto each adsorption column (one side); ΔQ represents the equilibriumadsorption amount amplitude which results under the conditions foradsorption and desorption, i.e., the adsorption amount difference(Q2−Q1); η_(c) represents adsorption amplitude efficiency, which showsthe proportion of the actual adsorption amplitude in the time betweenswitching operations to the equilibrium adsorption amplitude ΔQ; ΔHrepresents the latent heat of vaporization of water; τ represents thetime period between operations of switching to the adsorption mode ordesorption mode; and η_(h) represents heat mass efficiency for takingaccount of the heat mass loss caused by the temperature changes of theadsorbent and heat exchangers between the temperature of warm water andthe temperature of cooling water.

[0082] As stated above, R is 3 kW and W is 1.89 kg/2=0.95 kg. Aninvestigation which was made previously by us revealed that anappropriate value of τ is about 60 seconds, and it has been found thatthe values of ΔH, η_(c), and η_(h) are 2,500 kJ/kg, 0.6, and 0.85,respectively. Consequently, ΔQ is determined using equation (A).

ΔQ=R/W/η _(c) /ΔH·τ/η _(h)=3.0/0.95/0.6/2500·60/0.85=0.149 kg/kg

[0083] Namely, the adsorbent to be used in the adsorption heat pump formotor vehicles is one having a ΔQ of 0.15 g/g or larger, preferably 0.18g/g or larger, more preferably 0.20 g/g or larger.

[0084] Although the adsorbent was explained above on the assumption thatthe adsorption heat pump is applied to motor vehicles, it is a matter ofcourse that any adsorbent having the properties shown above can besufficiently applied to other applications including stationary use.

[0085] As a result of the investigations given above, the adsorbent foruse in an adsorption heat pump of the invention has been determined.

[0086] The adsorbent which shows a water adsorption amount difference of0.18 g/g or larger when the relative vapor pressure changes by 0.15 inthe range of from 0.05 to 0.30 is not particularly limited as long as itsatisfies the property requirement. However, zeolites are promisingmaterials. In zeolites, the pore volume, which contributes toadsorption, is governed by the framework density because zeolites arecrystalline. Zeolite 13X (framework density, 12.7 T/1,000 Å), which isan example of the zeolites having the lowest framework density, has amaximum adsorption amount of about 0.30 g/g. Consequently, when theadsorption amount as measured at the lower limit of relative vaporpressure of 0.05, which is specified in the invention, is larger than0.15 g/g, then it is impossible to obtain an adsorption amountdifference of 0.18 g/g. Therefore, the adsorption amount at a relativevapor pressure of 0.05, as determined from a water vapor adsorptionisotherm, is desirably 0.15 g/g or smaller, preferably 0.12 g/g orsmaller, more preferably 0.10 g/g or smaller, still more preferably 0.07g/g or smaller, and still further preferably 0.05 g/g or smaller.

[0087] <Adsorbent 2>

[0088] Another feature of an adsorbent in the invention resides in thatthe adsorbent is a water vapor adsorbent having a region in which theadsorption amount difference as determined with the following equationis 0.15 g/g or larger in the range in which the relative vapor pressure(φ2 b) during adsorption operation in the adsorption/desorption part isfrom 0.115 to 0.18 and the relative vapor pressure (φ1 b) duringdesorption operation in the adsorption/desorption part is from 0.1 to0.14:

Adsorption amount difference=Q 2−Q 1

[0089] wherein

[0090] Q1=adsorption amount at φ1 b as determined from a water vapordesorption isotherm obtained at a temperature (T3) used for desorptionoperation in the adsorption/desorption part

[0091] Q2=adsorption amount at φ2 b as determined from a water vaporadsorption isotherm obtained at a temperature (T4) used for adsorptionoperation in the adsorption/desorption part, provided that

[0092] φ1 b (relative vapor pressure during desorption operation in theadsorption/desorption part)=[equilibrium water vapor pressure at thetemperature of coolant (T2) cooling the condenser]/[equilibrium watervapor pressure at the temperature of heat medium (T1) heating theadsorption/desorption part]

[0093] φ2 b (relative vapor pressure during adsorption operation in theadsorption/desorption part)=[equilibrium vapor pressure at thetemperature of cold (T0) generated in the vaporizationpart]/[equilibrium vapor pressure at the temperature of coolant (T2)cooling the adsorption/desorption part]

[0094] (wherein T0=5 to 10° C., T1=T3=90° C., and T2=T4=40 to 45° C.).

[0095] Although the adsorption amount difference for the adsorbent inthe invention is thus specified, a more preferred adsorbent satisfiesthe requirement which is specified under any of the following conditions(A) to (C).

[0096] (A) T0 is 10° C. and T2 is 40° C.

[0097] (B) T0 is 5° C. and T2 is 40° C.

[0098] (C) T0 is 10° C. and T2 is 45° C.

[0099] The adsorbent performance described above will be explained belowby reference to FIG. 1.

[0100] First, an explanation is given on the case of FIG. 1 in which thecontrol valves 31 and 34 are closed and the control valves 32 and 34 areopened.

[0101] In this case, the adsorbent packed in the adsorption column 2adsorbs the water vapor supplied from the vaporizer 4 and thus heats up.During this adsorption, the adsorption column 2 is cooled and deprivedof heat by the heat medium (e.g., cooling water) which is passingthrough the heat medium pipes 211 and 21. The temperature of this heatmedium (cooling water), which is supplied through the pipe 211 forcooling the adsorption column 2 (adsorption/desorption part), isreferred to as T2.

[0102] On the other hand, the temperature of the vaporizer 4 isregulated for the purpose of generating cold. The adsorption-siderelative vapor pressure φ2 b in this operation is defined by thefollowing equation.

Adsorption-side relative vapor pressure φ2 b=[equilibrium water vaporpressure (T 0)]/[equilibrium water vapor pressure (T 2)]

[0103] Equilibrium water vapor pressure (T0): equilibrium water vaporpressure at the temperature T0 of the vaporizer 4

[0104] Equilibrium water vapor pressure (T2): equilibrium water vaporpressure at the temperature T2 of the heat medium in the adsorptioncolumn 2

[0105] On the other hand, the adsorption column 1 during this operationis in the desorption (regeneration) mode. The adsorbent packed in theadsorption column 1 is regenerated by a regenerating heat source(temperature of the heat medium for heating the adsorption/desorptionpart; this temperature is referred to as T1). The condenser 5 is cooledwith the cooling water supplied through the heat medium pipe 51 andthereby condenses water vapor. The desorption-side relative vaporpressure φ1 in this operation is defined by the following equation.

Desorption-side relative vapor pressure φ1 b=[equilibrium vapor pressure(T 2)]/[equilibrium vapor pressure (T 1)]

[0106] Equilibrium vapor pressure (T2): equilibrium vapor pressure atthe temperature of the condenser 5 (=equilibrium vapor pressure at thetemperature T2 of the heat medium in the adsorption column 2)

[0107] Equilibrium vapor pressure (T1): equilibrium vapor pressure atthe temperature (T1) of the regenerating heat source in the adsorptioncolumn 1

[0108] An important point here is that in an adsorption column, thetemperature during adsorption differs from the temperature duringdesorption (regeneration). Consequently, in the invention, theadsorption amount difference is determined from a desorption isothermobtained at a desorption temperature and from an adsorption isothermobtained at an adsorption isotherm. Specifically, it is calculated usingthe following equation.

Adsorption amount difference=Q 2−Q 1

[0109] wherein

[0110] Q1=adsorption amount at φ1 b as determined from a water vapordesorption isotherm obtained at a temperature (T3) used for desorptionoperation in the desorption part

[0111] Q2=adsorption amount at φ2 b as determined from a water vaporadsorption isotherm obtained at a temperature (T4) used for adsorptionoperation in the adsorption/desorption part, provided that

[0112] φ1 b (relative vapor pressure during desorption operation in theadsorption/desorption part)=[equilibrium water vapor pressure at thetemperature of coolant (T2) cooling the condenser]/[equilibrium watervapor pressure at the temperature of heat medium (T1) heating theadsorption/desorption part]

[0113] φ2 b (relative vapor pressure during adsorption operation in theadsorption/desorption part)=[equilibrium vapor pressure at thetemperature of cold (T0) generated in the vaporizationpart]/[equilibrium vapor pressure at the temperature of coolant (T2)cooling the adsorption/desorption part]

[0114] (wherein T0=5 to 10° C., T1=T3=90° C., and T2=T4=40 to 45° C.).

[0115] The adsorbent according to the invention has an adsorption amountdifference, as determined with the equation shown above, of 0.15 g/g orlarger, preferably 0.18 g/g or larger. The larger the adsorption amountdifference, the more the adsorbent is preferred. However, when availablematerial sources which satisfy such performance are taken into account,the adsorption amount difference is usually 0.50 g/g or smaller,practically 0.40 g/g or smaller, especially 0.35 g/g or smaller.

[0116] Specifically, the adsorption amount difference is determinedthrough measurements made, for example, under (1) conditions in which T0is 10° C. and T2 is 40° C., (2) conditions in which T0 is 5° C. and T2is 40° C., or (3) conditions in which T0 is 1° C. and T2 is 45° C. Theadsorption amount difference thus determined may be any value not below0.15 g/g.

[0117] The necessity of the adsorption amount difference of 0.15 g/g orlarger is derived from the following investigation, which is made on thesupposition that the adsorption heat pump is applied to motor vehicles.

[0118] <<Adsorption Temperature, Description Temperature>>

[0119] First, an adsorption isotherm and a desorption isotherm areobtained at an adsorption temperature and a desorption temperature,respectively, because the adsorption amount depends on the temperatureduring adsorption and the temperature during desorption as stated above.

[0120] During adsorption, the adsorption column is cooled with coolingwater in order to inhibit the column from being heated up by adsorptionheat. Because of this, the temperature of the cooling water (T2) isalmost equal to the adsorption temperature (T4). On the other hand,during desorption, the adsorption column requires desorption heat andthe temperature of warm water (T1) is equal to the desorptiontemperature (T3).

[0121] Incidentally, heat medium temperatures in the adsorption heatpump are as follows: (1) the warm-water temperature is about 90° C.because it is a temperature obtained with the engine-cooling water; (2)the cooling temperature is about from 40° C. to 45° C. because it is atemperature obtained by heat exchange with the outside air; and (3) thetemperature of cold water necessary for generating a cold wind is aboutfrom 5 to 10° C. Namely, the cold-water temperature is about from 5 to10° C. on the assumption that the adsorption heat pump is applied togeneral motor vehicles in Japan. The cooling temperature is about 40° C.in Japan, and is about 45° C. in regions where the outside airtemperature is high.

[0122] Consequently, the adsorption temperature (T4) is about from 40°C. to 45° C. and the desorption temperature (T3) is about 90° C.

[0123] In the invention, the adsorption temperature and the desorptiontemperature are employed as indexes to adsorbent performance. Theadsorbent is one which satisfies the requirement that the adsorptionamount difference, as determined from at least one of adsorptionisotherms obtained at adsorption temperatures of from 40° C. to 45° C.and from a desorption isotherm obtained at a desorption temperature of90° C., is 0.15 g/g or larger.

[0124] <<Adsorption Amount Difference>>

[0125] The adsorption amount difference (0.15 g/g or larger) isdetermined in the same manner as for adsorbent 1.

[0126] Although the adsorbent was explained above on the assumption thatthe adsorption heat pump is applied to motor vehicles, it is a matter ofcourse that any adsorbent having the properties described above can besufficiently applied to other applications including stationary use.

[0127] It is noted that the adsorption amount difference according tothe invention is satisfied in the range in which the relative vaporpressure during adsorption operation φ2 b in the adsorption/desorptionpart is from 0.115 to 0.18 and the relative vapor pressure duringdesorption operation φ1 b in the adsorption/desorption part is from 0.1to 0.14. This range roughly corresponds to the range of operatingrelative vapor pressures for adsorption heat pumps.

[0128] When the adsorbent has a region in which the adsorption amountdifference is 0.15 g/g or larger in the range in which φ1 b and φ2 b arefrom 0.115 to 0.18 and φ1 b is equal to or higher than φ2 b, then thisadsorbent is advantageous because the adsorption heat pump can beoperated therewith even under severe temperature conditions which havebeen thought to be unable to be used for operating adsorption heatpumps.

[0129] Adsorbent 2 described above is selected from zeolites containingat least aluminum and phosphorus in the framework structure.

[0130] <Adsorbent Materials>

[0131] The adsorbents in the invention preferably are zeolites.Especially preferred is a zeolite containing aluminum, phosphorus, and aheteroatom in the framework structure. The zeolites here may be naturalzeolites or artificial zeolites. Examples of the artificial zeolitesinclude the aluminosilicates, aluminophosphates, and the like defined byInternational Zeolite Association (IZA).

[0132] Of the aluminophosphates, ALPO₄-5 is unsuitable for use as anadsorbent in the invention because it shows hydrophobic adsorptionproperties. For making this material suitable for use as an adsorbent inthe invention, it is preferred to replace part of the aluminum andphosphorus with a heteroatom, e.g., silicon, lithium, magnesium,titanium, zirconium, vanadium, chromium, manganese, iron, cobalt,nickel, palladium, copper, zinc, gallium, germanium, arsenic, tin,calcium, or boron, in order to impart hydrophilicity.

[0133] Preferred of those are zeolites formed by replacing part of thealuminum and phosphorus with silicon, magnesium, titanium, zirconium,iron, cobalt, zinc, gallium, or boron. Most preferred of these arezeolites formed by replacement with silicon; this kind of zeolites arecommonly called SAPO. The heteroatoms thus incorporated may be of two ormore kinds.

[0134] A preferred aluminophosphate among the zeolites usable asadsorbents in the invention is a zeolite which contains aluminum,phosphorus, and a heteroatom in the framework structure and in which theproportions of the atoms present are represented by the followingexpressions (1), (2), and (3):

0.001≦x≦0.3  (1)

[0135] (wherein x represents the molar proportion of the heteroatom inthe framework structure to the sum of aluminum, phosphorus, and theheteroatom in the framework structure);

0.3≦y≦0.6  (2)

[0136] (wherein y represents the molar proportion of aluminum in theframework structure to the sum of aluminum, phosphorus, and theheteroatom in the framework structure);

0.3≦z≦0.6  (3)

[0137] (wherein z represents the molar proportion of phosphorus in theframework structure to the sum of aluminum, phosphorus, and theheteroatom in the framework structure). Among the proportions of atomspresent, the proportion of the heteroatom is preferably represented bythe following expression (4):

0.003≦x≦0.25  (4)

[0138] (wherein x is as defined above) and more preferably representedby the following expression (5):

0.005≦x≦0.2  (5)

[0139] (wherein x is as defined above).

[0140] Preferred of the zeolites containing aluminum, phosphorus, and aheteroatom in the framework structure are ones in which the heteroatomis silicon atom and which give a ²⁹Si-MAS-NMR spectrum in which theintegrated intensity area for the signals at from −108 ppm to −123 ppmis not more than 10% based on the integrated intensity area for thesignals at from −70 ppm to −123 ppm. That integrated intensity arearatio is more preferably 9.5% or less, especially preferably 9% or less.

[0141] Furthermore, the zeolites preferably are ones which give a²⁹Si-MAS-NMR spectrum in which the integrated intensity area for thesignals at from −70 ppm to −92 ppm is not less than 25% based on theintegrated intensity area for the signals at from −70 ppm to −123 ppm.That integrated intensity area ratio is more preferably 50% or more.

[0142] The ²⁹Si-MAS-NMR spectra in the invention are ones obtained by amethod in which a sample is stored in a water-containing desiccator atroom temperature over a whole day and night to cause the sample toadsorb water to saturation and this sample is examined under thefollowing conditions using tetramethylsilane as a reference material.

[0143] Apparatus: Chemagnetic CMX-400

[0144] Probe: 7.5 mm MAS Probe

[0145] Resonance frequency: 79.445 MHz

[0146] Pulse duration: 5.0 microsecond

[0147] Pulse series: single pulse

[0148] Waiting time: 60 seconds

[0149] Revolution speed: 4,000 rps

[0150] A ²⁹Si-MAS-NMR spectrum for a zeolite gives information about thecombined state of silicon in the zeolite. From the positions anddistribution of peaks, the combined state of silicon can be understood.

[0151] Although a preferred zeolite in the invention contains aluminum,phosphorus, and silicon, the silicon atoms in the zeolite are present asSiO₂ units. In a ²⁹Si-MAS-NMR spectrum, the peak appearing at around −90ppm is attributable to silicon atoms each bonded, through oxygen atoms,to four atoms other than silicon atoms. In contrast, the peak appearingat around −110 ppm is attributable to silicon atoms each bonded to foursilicon atoms through oxygen atoms. Namely, when a zeolite gives aspectrum in which the peak at around −110 ppm has a high intensity, thismeans that silicon atoms have gathered together, i.e., the silicon atomsin the zeolite are in a lowly dispersed state.

[0152] Zeolites giving such a spectrum tend to satisfy the requirementconcerning adsorption properties according to the invention. This may bebecause the dispersion of silicon influences the adsorption propertiesof the zeolites and a zeolite having high silicon dispersion exhibitsperformance especially suitable for adsorbents for adsorption heat pumpsas will be described later.

[0153] On the other hand, the zeolite to be used as an adsorbent in theinvention preferably is one having a framework density of from 10.0T/1,000 Å³ to 16.0 T/1,000 Å³. More preferred is a zeolite in which theframework density is in the range of from 10.0 T/1,000 Å³ to 15.0T/1,000 Å³. The term framework density herein means the number offramework-constituting elements other than oxygen per 1,000 Å³ of thezeolite; this value is governed by the structure of the zeolite.

[0154] Framework density correlates to pore volume. In general, when theframework density is high, the pore volume is small and this tends toresult in an insufficient adsorption amount and poor performance in useas an adsorbent for adsorption heat pumps. On the other hand, when theframework density is low, the volume of pores capable of adsorption islarge. Although this adsorbent has an increased adsorption amount, ittends to have a reduced density and poor strength.

[0155] Examples of zeolite structures satisfying the requirementconcerning framework density include AFG, MER, LIO, LOS, PHI, BOG, ERI,OFF, PAU, EAB, AFT, LEV, LTN, AEI, AFR, AFX, GIS, KFI, CHA, GME, THO,MEI, VFI, AFS, LTA, FAU, RHO, DFO, EMT, AFY, and *BEA in terms of thecode defined by IZA. Preferred examples thereof include AEI, GIS, KFI,CHA, GME, VFI, AFS, LTA, FAU, RHO, EMT, AFY, and *BEA. Preferred arezeolites having the structure CHA, AEI, or ERI. Especially preferred ofthese is the structure CHA.

[0156] The structure of a zeolite is determined by obtaining an XRDpattern through powder XRD (powder X-ray diffraction) and comparing thispattern with XRD patterns given in Collection Of Simulated XRD PowderPatterns For Zeolites (1996, ELSEVIER).

[0157] Furthermore, the relationship between structure and frameworkdensity is described in Atlas Of Zeolite Structure Types (1996,ELSEVIER), IZA. Framework density can hence be determined from thestructure.

[0158] For example, the silicoaluminophosphate known as SAPO-34, whichcontains atoms of elements including silicon incorporated in the zeoliteframework structure, can be used as an aluminophosphate of the CHAstructure. Thus, desired adsorption performance can be imparted.

[0159] Although the adsorbents in the invention preferably are zeolitescontaining aluminum, phosphorus, and a heteroatom in the frameworkstructure, the zeolites may be aluminosilicates as long as they have theadsorbent properties described above. In this case, part of the siliconand aluminum (or with respect to the aluminum, all of it) in theframework may have been replaced with other atoms, e.g., magnesium,titanium, zirconium, vanadium, chromium, manganese, iron, cobalt, zinc,gallium, tin, or boron. In case where aluminosilicates have too small asilicon/aluminum molar ratio, abrupt adsorption occurs in a region oftoo low humidities as in the case of zeolite 13X. In case where thatratio is too large, the aluminosilicates are too hydrophobic tosufficiently adsorb water. Consequently, the zeolite to be used in theinvention has a silicon/aluminum molar ratio of generally from 4 to 20,preferably from 4.5 to 18, more preferably from 5 to 16.

[0160] The zeolites described above include ones having cation speciesexchangeable with other cations. In this case, examples of the cationspecies include proton, alkali elements such as Li and Na, alkalineearth elements such as Mg and Ca, rare earth elements such as La and Ce,transition metals such as Fe, Co, and Ni, and the like. Preferred areproton, alkali elements, alkaline earth elements, and rare earthelements. More preferred are proton, Li, Na, K, Mg, and Ca. Thesezeolites may be used alone or used in combination of two or more thereofor in combination with another material such as silica, alumina, activecarbon, or clay.

[0161] The adsorbents in the invention have a pore diameter ofpreferably 3 Å or larger, specially 3.1 Å or larger. The pore diameterthereof is preferably 10 Å or smaller, especially 8 Å or smaller, morepreferably 7.5 Å or smaller. In case where the pore diameter thereof istoo large, there is the possibility that adsorption might not occur atdesired relative humidities. In case where the pore diameter thereof istoo small, molecules of water used as an adsorbate tend to less diffusein the adsorbent.

[0162] The adsorbents in the invention preferably have a heat ofadsorption of from 40 kJ/mol to 65 kJ/mol. This is becausesusceptibility to desorption also is an important property foradsorbents for adsorption heat pumps in which it is required thatdesorption occurs with a heat source of 100° C. or lower. Susceptibilityto desorption is inversely proportional to adsorption force.Consequently, the heat of adsorption, which is an index to the degree ofadsorption, desirably is close to the latent heat of condensation ofwater. The heat of adsorption for the adsorbents, which is not lowerthan the latent heat of condensation of water, may be 40 kJ/mol orhigher. In case where the heat of adsorption is too high, desorptionwith a heat source of 100° C. or lower tends to be difficult.Consequently, a zeolite having a heat of adsorption not lower than thelatent heat of condensation of water and not higher than 65 kJ/mol ispreferred. In this description, a differential heat of adsorption wasdetermined through simultaneous measurements of adsorption amount andheat of adsorption (measuring temperature, 25° C.) by the methoddescribed in a document (Colloid Polym Sci, 277 (1999) pp.83-88), andthe differential heat of adsorption for the adsorption amount range offrom 0.005 mol/g to 0.01 mol/g was taken as the heat of adsorption.

[0163] An especially preferred example of the adsorbents for use in theinvention is SAPO 34, which is an SAPO (silicoaluminophosphate) in a CHAform (framework density=14.6 T/1,000 Å³).

[0164] Processes for producing the zeolite in the invention are notparticularly limited as long as the zeolite has the properties describedabove. For example, the zeolite can be produced in the following manneraccording to the method described in Japanese Patent Publication No.37007/1992, Japanese Patent Publication No. 21844/1993, Japanese PatentPublication No. 51533/1993, U.S. Pat. No. 4,440,871, etc. A method ofsynthesizing SAPO-34 is described in U.S. Pat. No. 4,440,871.

[0165] In particular, examples of processes for producing the preferredzeolite containing aluminum, phosphorus, and silicon atoms in theframework structure include the following method.

[0166] First, an aluminum source, silica source, phosphate source, andtemplate are mixed together to prepare an aqueous gel.

[0167] As the aluminum source is used pseudoboehmite, aluminumisopropoxide, aluminum hydroxide, alumina sol, sodium aluminate, or thelike.

[0168] As the silica source is used fumed silica, silica sol, colloidalsilica, water glass, ethyl silicate, methyl silicate, or the like.

[0169] As the phosphate source is used phosphoric acid. Aluminumphosphate also is usable.

[0170] As the template is used a quaternary ammonium salt such as atetramethylammonium, tetraethylammonium, tetrapropylammonium, ortetrabutylammonium, or a primary amine, secondary amine, tertiary amine,or polyamine, such as morpholine, di-n-propylamine, tripropylamine,triethylamine, triethanolamine, piperidine, cyclohexylamine,2-methylpyridine, N,N-dimethylbenzylamine, N,N-diethylethanolamine,dicyclohexylamine, N,N-dimethylethanolamine, choline,N,N′-dimethylpiperazine, 1,4-diazabicyclo(2,2,2)octane,N-methyldiethanolamine, N-methylethanolamine, N-methylpiperidine,3-methylpiperidine, N-methylcyclohexylamine, 3-methylpyridine,4-methylpyridine, quinuclidine,N,N′-dimethyl-1,4-diazabicyclo(2,2,2)-octaneion, di-n-butylamine,neopentylamine, di-n-pentylamine, isopropylamine, t-butylamine,ethylenediamine, pyrrolidine, 2-imidazolidone, diisopropylethylamine, ordimethylcyclohexylamine.

[0171] The sequence of mixing an aluminum source, silica source,phosphate source, and template varies depending on conditions. Ingeneral, however, a phosphate source is first mixed with an aluminumsource, and the resultant mixture is mixed with a silica source and atemplate. The composition of the aqueous gel is generally such that0.02<SiO₂/P₂O₅<20 and 0.02<SiO₂/Al₂O₃<20, preferably such that0.04<SiO₂/P₂O₅<10 and 0.04<SiO₂/Al₂O₃<10, in terms of oxide molar ratio.The pH of the aqueous gel is from 5 to 10, preferably from 6 to 9.

[0172] Ingredients other than those shown above may suitably coexist inthe aqueous gel. Examples of such ingredients include hydroxides andsalts of alkali metals or alkaline earth metals and hydrophilic organicsolvents such as alcohols.

[0173] The aqueous gel prepared is placed in a pressure vessel and heldat a given temperature, while being stirred or allowed to stand, underthe pressure generated by the gel itself or under a gas pressure whichdoes not inhibit crystallization. Thus, hydrothermal synthesis isconducted.

[0174] Conditions for the hydrothermal synthesis include a temperatureof generally from 100° C. to 300° C., preferably from 120° C. to 250° C.The reaction time is generally from 5 hours to 30 days, preferably from10 hours to 15 days.

[0175] After the hydrothermal synthesis, the reaction product isseparated, washed with water, and dried. The organic matters containedtherein are removed by burning or another method to obtain a zeolite.

[0176] In the case where the zeolite is processed for use as a watervapor adsorbent, care should be taken not to reduce the adsorptionperformance of the zeolite. In general, however, an inorganic bindersuch as alumina or silica is used to mold the zeolite.

[0177] Silica gel, mesoporous silica, alumina, active carbon, clay, orthe like may be incorporated into the adsorbent besides the zeoliteaccording to the invention in order to impart desired water vaporadsorption properties to the adsorbent. However, from the standpoint ofobtaining satisfactory adsorption properties at low relative vaporpressures, the proportion of the zeolite in the adsorbent according tothe invention is generally 60% by weight or higher, preferably 70% byweight or higher, more preferably 80% by weight or higher. From thestandpoint of adsorption properties, it is most preferred to use thezeolite alone as a water vapor adsorbent.

[0178] For application to an adsorption heat pump or the like, theadsorbent is used after being processed by a known method so as to havea given strength, particle diameter, and shape according to theapplication. For example, the size of adsorbent particles suitable foruse in adsorption heat pumps is about from 0.05 mm to 2 mm as disclosedin Japanese Patent Laid-Open No. 2001-38188. In the case where theadsorbent is bonded to an adsorption core with an adhesive as disclosedin Japanese Patent Laid-Open No. 2000-18767, it is necessary that theadsorbent particles have such a strength that they do not break whenmixed with the adhesive and dispersed.

[0179] <Method of Operation>

[0180] A method of operating an adsorption heat pump is explained withreference to FIG. 1. In the first step, the control valves 31 and 34 areclosed and the control valves 32 and 33 are opened to thereby operatethe adsorption column 1 and the adsorption column 2 in the regenerationmode and the adsorption mode, respectively. Furthermore, the switchingvalves 115, 116, 215, and 216 are regulated to pass warm water andcooling water through the heat medium pipe 11 and heat medium pipe 21,respectively.

[0181] For example, in the case where the adsorption column 2 is to becooled, cooling water which has been cooled by heat exchange with theoutside air, river water, or the like by means of a heat exchanger,e.g., a cooling column, is introduced through the heat medium pipe 21 tocool the adsorption column 2 usually to about 30 to 40° C. Furthermore,the control valve 32 is opened and, as a result, the water present inthe vaporizer 4 vaporizes and the resultant water vapor flows into theadsorption column 2 and is adsorbed onto the adsorbent. The movement ofwater vapor occurs based on the difference between the saturation vaporpressure at the vaporization temperature and the adsorption equilibriumpressur corresponding to the adsorbent temperature (generally from 20 to50° C., preferably from 20 to 45° C., more preferably from 30 to 40°C.). As a result, cold, i.e., a cooling output, corresponding the heatof vaporization is obtained in the vaporizer 4. The adsorption-siderelative vapor pressure (φ2 a is determined from the relationshipbetween the temperature of cooling water for the adsorption column andthe temperature of the cold water yielded in the vaporizer (φ2 a isobtained by diving the equilibrium vapor pressure of the adsorbate atthe temperature of the cold water yielded in the vaporizer by theequilibrium vapor pressure of the adsorbate at the temperature of thecooling water in the adsorption column). It is, however, preferred tooperate so that φ2 a is higher than the relative vapor pressures atwhich the adsorbent specified in the invention adsorbs a maximum amountof water vapor. This is because when φ2 a is lower than the relativevapor pressures at which the adsorbent specified in the inventionadsorbs a maximum amount of water vapor, then the adsorbing ability ofthe adsorbent cannot be effectively utilized, resulting in an impairedoperation efficiency. Although φ2 a can be suitably selected accordingto the ambient temperature, etc., the adsorption heat pump is operatedunder such temperature conditions that the adsorption amount at φ2 a isgenerally 0.20 or larger, preferably 0.29 or larger, more preferably0.30 or larger. This adsorption amount is determined from an adsorptionisotherm obtained at 25° C.

[0182] The adsorption column 1 in the regeneration mode is heated withwarm water of generally from 40 to 100° C., preferably from 50 to 98°C., more preferably from 60 to 95° C., and comes to have an equilibriumvapor pressure corresponding to the temperature range shown above.Condensation thus occurs at the saturation vapor pressure at acondensation temperature of from 30 to 40° C. in the condenser 5 (thistemperature is equal to the temperature of the cooling water with whichthe condenser is being cooled). Water vapor moves from the adsorptioncolumn 1 to the condenser 5 and is condensed to water. The water isreturned to the vaporizer 4 through the return piping 3. Thedesorption-side relative vapor pressure φ1 a is determined from therelationship between the temperature of cooling water for the condenserand the temperature of warm water (φ1 a is obtained by dividing theequilibrium vapor pressure of the adsorbate at the temperature of thecooling water for the condenser by the equilibrium vapor pressure of theadsorbate at the temperature of the warm water). It is, however,preferred to operate so that φ1 a is lower than the relative vaporpressers at which the adsorbent abruptly adsorbs water vapor. Althoughφ1 a can be suitably selected according to the ambient temperature,etc., the adsorption heat pump is operated under such temperatureconditions that the adsorption amount at φ1 a is generally 0.06 orsmaller, preferably 0.05 or smaller. Incidentally, the adsorption heatpump is operated so that the difference between the adsorbate adsorptionamount at φ1 a and the adsorbate adsorption amount at φ2 a is generally0.18 g/g or larger, preferably 0.20 g/g or larger, more preferably 0.25g/g or larger. The first step is conducted in the manner describedabove.

[0183] In the subsequent step as the second step, the control valves 31to 34 and the switching valves 115, 116, 215, and 216 are switched so asto operate the adsorption column 1 and the adsorption column 2 in theadsorption mode and the regeneration mode, respectively, whereby cold,i.e., a cooling output, can be obtained from the vaporizer 4. Byalternately conducting the first and second steps described above, theadsorption heat pump is continuously operated.

[0184] An operation method was explained above with respect to anadsorption heat pump having two adsorption columns. However, any desirednumber of adsorption columns may be disposed as long as any of theadsorption columns can be made to retain the state of being capable ofadsorbing the adsorbate by suitably desorbing the adsorbate adsorbed onthe adsorbent.

[0185] Adsorption heat pumps utilize as a driving force the ability ofan adsorbent to adsorb and release an adsorbate. Although water,ethanol, acetone, and the like can be used as the adsorbate inadsorption heat pumps, water is most preferred from the standpoints ofsafety, cost, and the large quantity of latent head of vaporization.

[0186] The adsorption heat pumps of the invention employ an adsorbentcapable of undergoing a large change in adsorption amount with a changein relative vapor pressure in a narrow range. The adsorption heat pumpsare hence suitable for use in applications where apparatus sizereduction is required and adsorbent packing amounts are limited, suchas, e.g., air conditioning systems for vehicles.

EXAMPLES

[0187] The invention will be explained below in detail by reference toExamples, but the invention should not be construed as being limited bythe following Examples in any way.

[0188] In the following Examples, water vapor adsorption isotherms at25° C. were obtained by examining the adsorbents for water vaporadsorption properties under the following conditions.

[0189] Adsorption isotherm analyzer: Belsorb 18 (manufactured by BelJapan Inc.)

[0190] Temperature of high-temperature air chamber: 50° C.

[0191] Adsorption temperature: 25° C.

[0192] Initial pressure introduced: 3.0 Torr

[0193] Number of points for setting pressure introduced:0

[0194] Saturated vapor pressure: 23.76 mmHg

[0195] Equilibrium time: 500 sec

[0196] Pretreatment: 300° C. 5-hour evacuation

[0197] A measurement for determining the differential heat of adsorptionwas made under the following conditions.

[0198] Measuring apparatus: calorimeter and adsorption amount-measuringapparatus (manufactured by Tokyo Riko)

[0199] Temperature of measurement part: 25° C.

[0200] Temperature of thermostatic chamber for vapor introduction: 30°C.

Example 1

[0201] A water vapor adsorption isotherm (25° C.) for SAPO-34(manufactured by UOP LLC) is shown in FIG. 1. It can be seen from FIG. 1that the adsorbent abruptly adsorbs water vapor at relative vaporpressures of from 0.07 to 0.10, and that the change in adsorption amountin the relative vapor pressure range of from 0.05 to 0.20 is 0.25 g/g.

[0202] SAPO-34 is a CHA-form silicoaluminophosphate; the CHA form has aframework density of 14.6 T/1,000 Å3 and a pore diameter of 3.8 Å.

[0203] A ²⁹Si-MAS-NMR chart for SAPO-34 (manufactured by UOP LLC) isshown in FIG. 3. The spectral chart shows that the integrated intensityarea for the signals at from −108 ppm to −123 ppm and the integratedintensity area for the signals at from −70 ppm to −92 ppm were 0.6% and85.9%, respectively, based on the integrated intensity area for thesignals at from −70 ppm to −123 ppm. Furthermore, the heat of adsorptionwas found to be 58.6 kJ/mol.

Example 2

[0204] A CHA-form silicoaluminophosphate was produced in the followingmanner according to the method described in Japanese Patent PublicationNo. 37007/1992.

[0205] To 18 g of water were gradually added 15.4 g of 85% phosphoricacid and 9.2 g of pseudoboehmite (containing 25% water; manufactured byCondea). The resultant mixture was stirred. Ten grams of water wasfurther added thereto and this mixture was stirred for 1 hour. Thisliquid is referred to as liquid A. Separately from liquid A, a liquidwas prepared by mixing 4.1 g of fumed silica (Aerosil 200), 11.6 g ofmorpholine, and 15 g of water. This liquid was gradually added to liquidA. Thereto was further added 24 g of water. This mixture was stirred for3 hours.

[0206] The mixture obtained was introduced into a 200-cc stainless-steelautoclave containing a Teflon inner cylinder, and reacted by beingallowed to stand at 200° C. for 24 hours. After the reaction, thereaction mixture was cooled and the supernatant was removed bydecantation to recover the precipitate. The precipitate obtained waswashed with water three times, subsequently taken out by filtration, anddried at 120° C. This precipitate was burned at 550° C. for 6 hours inan air stream to obtain a zeolite.

[0207] Analysis by powder XRD revealed that this zeolite was a CHA-form(framework density=14.6 T/1,000 Å³) silicoaluminophosphate. Theframework density was determined from the structure by reference toAtlas Of Zeolite Structure Types (1996, ELSEVIER), IZA. A sample wasdissolved in an aqueous hydrochloric acid solution with heating and thissolution was subjected to ICP analysis. As a result, the proportions(molar proportions) of the aluminum, phosphorus, and silicon in theframework structure to the sum of these components were found to be asfollows: the proportion of silicon was 0.13, that of aluminum was 0.49,and that of phosphorus was 0.38.

[0208] An adsorption isotherm at 25° C. for this zeolite is shown inFIG. 4. It can be seen from FIG. 4 that this zeolite abruptly adsorbswater vapor at relative vapor pressures of from 0.07 to 0.10, and thatthe change in adsorption amount in the relative vapor pressure range offrom 0.05 to 0.20 is 0.25 g/g.

[0209] A ²⁹Si-MAS-NMR spectral chart for this zeolite is shown in FIG.5. In this ²⁹Si-NMR spectrum, the integrated intensity area for thesignals at from −108 ppm to −123 ppm and the integrated intensity areafor the signals at from −70 ppm to −92 ppm were 9.2% and 52.6%,respectively, based on the integrated intensity area for the signals atfrom −70 ppm to −123 ppm.

Example 3

[0210] To 128 g of water was added 72 g of aluminum isopropoxide. Afterthe mixture was stirred, 38.76 g of 85% phosphoric acid was addedthereto and this mixture was stirred for 1 hour. To this solution wasadded 1.2 g of fumed silica (Aerosil 200), followed by 89.3 g of 35%aqueous tetraethylammonium hydroxide (TEAOH). The resultant mixture wasstirred for 3 hours. This mixture was introduced into a 500-ccstainless-steel autoclave containing a Teflon inner cylinder, andreacted at 185° C. for 60 hours with stirring at 100 rpm. After thereaction, the reaction mixture was cooled and the reaction product wasseparated by centrifuging, washed with water, and dried at 120° C. Thisreaction product was burned at 550° C. for 6 hours in an air stream toobtain a zeolite.

[0211] Analysis by powder XRD revealed that this zeolite was a CHA-formsilicoaluminophosphate (framework density=14.6 T/1,000 Å³). A sample wasdissolved in an aqueous hydrochloric acid solution with heating and thissolution was subjected to ICP analysis. As a result, the proportions(molar proportions) of the aluminum, phosphorus, and silicon in theframework structure to the sum of these components were found to be asfollows: the proportion of silicon was 0.03, that of aluminum was 0.50,and that of phosphorus was 0.47.

[0212] An adsorption isotherm at 25° C. for this zeolite is shown inFIG. 6. It can be seen from FIG. 6 that this zeolite shows an adsorptionisotherm similar to that of the zeolite of Example 2. Namely, thiszeolite abruptly adsorbs water vapor at relative vapor pressures of from0.07 to 0.10, and the change in adsorption amount in the relative vaporpressure range of from 0.05 to 0.20 is 0.23 g/g.

[0213] The heat of adsorption was 58.2 kJ/mol.

Example 4

[0214] SAPO-34 (manufactured by UOP LLC) was examined with an adsorptionisotherm analyzer (Belsorb 18, manufactured by Bel Japan Inc.). In FIG.7 is shown an adsorption-process water vapor adsorption isotherm at 40°C. for SAPO-34. The examination for adsorption isotherm was conductedunder the conditions of a high-temperature air chamber temperature of50° C., adsorption temperature of 40° C., initial pressure introduced of3.0 Torr, number of points for setting pressure introduced of 0,saturated vapor pressure of 55.33 mmHg, and equilibrium time of 500seconds.

[0215] On the other hand, a desorption-process adsorption isotherm wasobtained with a gravimetric-method adsorption amount analyzer includinga magnetic levitation balance (manufactured by Bel Japan Inc.) and,connected thereto, a vapor introduction part comprising a gas generationpart, pressure measurement part, and gas discharge part which weredisposed in a thermostatic air chamber. In obtaining adesorption-process adsorption isotherm, water vapor was discharged 50Torr by 50 Torr at a high-temperature air chamber temperature of 120° C.and a desorption temperature of 90° C. to determine the weight changes.The results are shown in FIG. 7.

[0216] On the assumption that the adsorbent is applied to an automotiveair conditioning system for general motor vehicles, the conditions mayinclude T1=90° C., T2=40° C., and T0=10° C. It can be seen that undersuch conditions, the desorption-side relative vapor pressure φ1 and theadsorption-side relative vapor pressure φ2 are 0.11 and 0.17,respectively, and the difference in adsorption amount between φ1 and φ2is 0.21 g/g. This value is higher than the target adsorption amountdifference of 0.15 g/g. It can hence be seen that the automotive airconditioning system sufficiently functions in general motor vehicles.

[0217] When T1=90° C., T2=40° C., and T0=5° C., then the difference inadsorption amount between φ1=0.11 and φ2=0.12 is 0.20 g/g. This value ishigher than th target adsorption amount difference of 0.15 g/g. It canhence be seen that the air conditioning system sufficiently functions.

[0218] Furthermore, it is presumed that in some regions, the coolingwater temperature T2 increases to around 45° C. due to severe ambientconditions. Conditions for obtaining T0=10° C. when T1=90° C. in thiscase are investigated. Belsorb 18 was used to obtain anadsorption-process adsorption isotherm at 45° C. This isotherm is shownin FIG. 8 together with a desorption-process adsorption isotherm at 90°C. The examination for obtaining the adsorption isotherm at 45° C. wasconducted under the conditions of a high-temperature air chambertemperature of 65° C., adsorption temperature of 45° C., initialpressure introduced of 3.0 Torr, number of points for setting pressureintroduced of 0, saturated vapor pressure of 55.33 mmHg, and equilibriumtime of 500 seconds. In the case where T1=90° C., T2=45° C., and T0=10°C., then the desorption-side relative humidity φ1 is 0.14, which ishigher than the adsorption-side relative humidity φ2 of 0.13.

[0219] It can be seen that even in such a case in which thedesorption-side relative vapor pressure is higher than theadsorption-side relative vapor pressure, an adsorption amount differenceof 0.16 g/g is obtained with the adsorbent of Example 4, which has atemperature dependence. The adsorption heat pump employing the watervapor adsorbent of Example 4 has proved to sufficiently work even inhigh-temperature regions.

Reference Example

[0220] To 173.4 g of water was added 115.3 g of 85% phosphoric acid.Thereto was gradually added 68 g of pseudoboehmite (containing 25%water; manufactured by Condea). This mixture was stirred for 3 hours.Thereto was added 30 g of fumed silica, followed by 87.2 g of morpholineand 242.3 g of water. The resultant mixture was stirred for 4.5 hours.This mixture was allowed to stand for aging at room temperatureovernight. The mixture was then introduced into an induction stirringtype 1-liter stainless-steel autoclave containing a Teflon innercylinder, and reacted at 200° C. for 24 hours with stirring at 60 rpm.After the reaction, the reaction mixture was cooled and the supernatantwas removed by decantation to recover the precipitate. The precipitatethus obtained was washed with water, taken out by filtration, and driedat 120° C. This precipitate was burned at 550° C. in an air stream toobtain a zeolite. Analysis by XRD revealed that this zeolite was in aCHA form. A sample was dissolved in an aqueous hydrochloric acidsolution with heating and this solution was subjected to ICP analysis.As a result, the proportions (molar proportions) of the aluminum,phosphorus, and silicon in the framework structure to the sum of thesecomponents were found to be as follows: the proportion of silicon was0.12, that of aluminum was 0.49, and that of phosphorus was 0.39.

[0221] An adsorption isotherm at 25° C. for this zeolite is shown inFIG. 9. It can be seen from FIG. 9 that this zeolite begins to abruptlyadsorb water vapor immediately after initiation of adsorption operationeven when the relative vapor pressure is still very low, and that thechange in adsorption amount in the relative vapor pressure range of from0.05 to 0.20 is as small as 0.1 g/g or less. These results show thatthis zeolite is unsuitable for use as an adsorbent for adsorption heatpumps.

[0222] This zeolite was subjected to Si-MAS-NMR analysis under the sameconditions, and the results thereof are shown in FIG. 10. In the²⁹Si-MAS-NMR spectrum, the integrated intensity area for the signals atfrom −108 ppm to −123 ppm and the integrated value for the signals atfrom −70 ppm to −92 ppm were 13.0% and 51.6%, respectively, based on theintegrated intensity area for the signals at from −70 ppm to −123 ppm.It can be seen from these results that even a CHA-formsilicoaluminophosphate is unsuitable for use as an adsorbent to beregenerated with a heat source of 100° C. or lower, when the peakappearing at around −110 ppm has a high intensity. The heat ofadsorption was 61.3 kJ/mol.

Comparative Example 1

[0223] A mesoporous molecular sieve (FSM-10) shows an adsorption amountdifference as large as 0.25 g/g in the relative vapor pressure range offrom 0.20 to 0.35 (according to Japanese Patent Laid-Open No.178292/1997, FIG. 14, graph 4 for FSM-10). However, it shows a smalladsorption amount when the relative vapor pressure is in range of from0.05 to 0.30, which is an example of conditions for the operation of theadsorption heat pumps of the invention. In this range, the relativevapor pressure region where the adsorbent shows a large adsorptionamount change is from 0.15 to 0.30. However, the adsorption amountdifference in this region is 0.08 g/g, showing that this adsorbent haspoor performance in adsorption heat pumps.

Comparative Example 2

[0224] A-form silica gel (manufactured by Fuji Silysia Chemical Ltd.),which is known as an adsorbent suitable for adsorption heat pumps, wasexamined with an adsorption isotherm analyzer (Belsorb 18, manufacturedby Bel Japan Inc.) to obtain a water vapor adsorption isotherm at anadsorption temperature of 25° C. This isotherm is shown in FIG. 11. Thismeasurement was made under the same conditions as for the SAPO-34 inExample 1. The adsorption isotherm for A-form silica gel given in FIG.11 shows that over the relative vapor pressure range of from 0 to 0.7,A-form silica gel gives an adsorption amount nearly proportional to therelative vapor pressure. However, in the relative vapor pressure rangeof from 0.15 to 0.30, A-form silica gel shows an adsorption amountchange as small as 0.08 g/g like the mesoporous molecular sieve andporous aluminum phosphate molecular sieves. Although adsorption heatpumps employing a silica gel as an adsorbent have been marketed, theapparatus size should be large because of this small adsorption amountdifference.

Comparative Example 3

[0225] In FIG. 12 is shown an adsorption isotherm for ALPO-5, which isAFI-form (framework density=17.5 T/1,000 Å³) zeolite as a porousaluminum phosphate molecular sieve (the isotherm is a quotation fromColloid Polym Sci, 277, pp.83-88 (1999), FIG. 1 (adsorption temperature30° C.)). The isotherm shows the following. ALPO-5 shows an abruptincrease in adsorption amount in the relative vapor pressure range offrom 0.25 to 0.40 and can be caused to adsorb and release the adsorbatein the relative vapor pressure range of from 0.05 to 0.3. However, theadsorption amount change in the relative vapor pressure range of from0.15 to 0.30 was as small as 0.14 g/g.

[0226] While the invention has been described in detail and withreference to specific embodiments thereof, it will be apparent to oneskilled in the art that various changes and modifications can be madetherein without departing from the spirit and scope thereof.

[0227] This application is based on a Japanese patent application filedon Feb. 21, 2001 (Application No. 2001-045677), Japanese patentapplication filed on Apr. 10, 2001 (Application No. 2001-111902),Japanese patent application filed on Jun. 25, 2001 (Application No.2001-191893), and Japanese patent application filed on Sep. 26, 2001(Application No. 2001-293990), the contents thereof being hereinincorporated by reference.

[0228] Industrial Applicability

[0229] One feature of the invention resides in that adsorbents havingthe properties described above are used. These adsorbents can be used inthe adsorption part of an adsorption heat pump. They give a large changein adsorption amount with a change in relative vapor pressure in anarrow range. Consequently, these adsorbents are suitable for use in anadsorption heat pump in which the adsorbent packing amount is limited,for example, an air conditioning system for motor vehicles.

[0230] In the adsorption heat pumps of the invention, the adsorbentshave a large difference in water adsorption amount inadsorption/desorption and can be regenerated (release the adsorbate) ata low temperature. Consequently, the adsorption heat pumps can beefficiently operated with a heat source having a lower temperature thanones heretofore in use. Furthermore, the adsorbents to be used in theinvention show a larger change in adsorption amount than the silica gelsand zeolites heretofore in use in the same relative vapor pressurerange. Consequently, the adsorption heat pumps can produce a higherdehumidifying effect when the adsorbents are used in almost the sameweight.

[0231] Namely, with the adsorbents according to the invention,adsorption heat pumps capable of operating with a heat source having arelatively low temperature of 100° C. or below can be provided.

1. An adsorption heat pump which comprises an adsorbate, anadsorption/desorption part having an adsorbent for adsorbateadsorption/desorption, a vaporization part for adsorbate vaporizationwhich has been connected to the adsorption/desorption part, and acondensation part for adsorbate condensation which has been connected tothe adsorption/desorption part, wherein the adsorbent, when examined at25° C., gives a water vapor adsorption isotherm which, in the relativevapor pressure range of from 0.05 to 0.30, has a relative vapor pressureregion in which a change in relative vapor pressure of 0.15 results in achange in water adsorption amount of 0.18 g/g or larger.
 2. Theadsorption heat pump as claimed in claim 1, wherein the adsorbentcomprises a zeolite having a framework density in the range of from 10.0T/1,000 Å³ to 16.0 T/1,000 Å³.
 3. The adsorption heat pump as claimed inclaim 2, wherein the adsorbent is an adsorbent having a pore diameter offrom 3 Å to 10 Å and a heat of adsorption of from 40 kJ/mol to 65kJ/mol.
 4. The adsorption heat pump as claimed in any one of claims 1 to3, characterized in that the adsorbent is a zeolite containing at leastaluminum, phosphorus, and a heteroatom in the framework structure. 5.The adsorption heat pump as claimed in claim 4, wherein the zeolite isone in which the proportions of atoms present therein are represented bythe following expressions (1), (2), and (3): 0.001≦x≦0.3  (1) (wherein xrepresents the molar proportion of the heteroatom in the frameworkstructure to the sum of aluminum, phosphorus, and the heteroatom in theframework structure); 0.3≦y≦0.6  (2) (wherein y represents the molarproportion of aluminum in the framework structure to the sum ofaluminum, phosphorus, and the heteroatom in the framework structure);0.3≦z≦0.6  (3) (wherein z represents the molar proportion of phosphorusin the framework structure to the sum of aluminum, phosphorus, and theheteroatom in the framework structure).
 6. The adsorption heat pump asclaimed in claim 4 or 5, wherein the heteroatom is silicon.
 7. Theadsorption heat pump as claimed in claim 4 or 5, wherein the heteroatomis silicon and the zeolite gives a ²⁹Si-MAS-NMR spectrum in which theintegrated intensity area for the signals at from −108 ppm to −123 ppmis not more than 10% based on the integrated intensity area for thesignals at from −70 ppm to −123 ppm.
 8. The adsorption heat pump asclaimed in claim 7, wherein the zeolite gives a ²⁹Si-MAS-NMR spectrum inwhich the integrated intensity area for the signals at from −70 ppm to−92 ppm is not less than 25% based on the integrated intensity area forthe signals at from −70 ppm to −123 ppm.
 9. The adsorption heat pump asclaimed in any one of claims 2 to 8, wherein the zeolite is one havingthe structure represented by CHA in terms of the code defined byInternational Zeolite Association (IZA).
 10. The adsorption heat pump asclaimed in any one of claims 2 to 9, wherein the adsorbent has a zeolitecontent of 60% by weight or higher based on the whole adsorbent.
 11. Theadsorption heat pump as claimed in any one of claims 1 to 10, whereinthe adsorbent, when examined at 25° C., gives a water vapor adsorptionisotherm in which the adsorption amount at a relative vapor pressure of0.05 is 0.15 g/g or less.
 12. An adsorption heat pump which comprises(a) an adsorbate, (b) an adsorption/desorption part having an adsorbentfor adsorbate adsorption/desorption, (c) a vaporization part foradsorbate vaporization which has been connected to theadsorption/desorption part, and (d) a condensation part for adsorbatecondensation which has been connected to the adsorption/desorption part,characterized in that (1) the adsorbent comprises a zeolite containingaluminum and phosphorus in the framework structure, and (2) theadsorbent is a water vapor adsorbent having a region in which theadsorption amount difference as determined with the following equationis 0.15 g/g or larger in the range in which the relative vapor pressureφ2 b during adsorption operation in the adsorption/desorption part isfrom 0.115 to 0.18 and the relative vapor pressure φb during desorptionoperation in the adsorption/desorption part is from 0.1 to 0.14:Adsorption amount difference=Q 2−Q 1 wherein Q1=adsorption amount at φ1b as determined from a water vapor desorption isotherm obtained at atemperature (T3) used for desorption operation in theadsorption/desorption part Q2=adsorption amount at φ2 b as determinedfrom a water vapor adsorption isotherm obtained at a temperature (T4)used for adsorption operation in the adsorption/desorption part,provided that φ1 b (relative vapor pressure during desorption operationin the adsorption/desorption part)=[equilibrium water vapor pressure atthe temperature of coolant (T2) cooling the condenser]/[equilibriumwater vapor pressure at the temperature of heat medium (T1) heating theadsorption/desorption part] φ2 b (relative vapor pressure duringadsorption operation in the adsorption/desorption part)=[equilibriumvapor pressure at the temperature of cold (T0) generated in thevaporization part]/[equilibrium vapor pressure at the temperature ofcoolant (T2) cooling the adsorption/desorption part] (wherein T0=5 to10° C., T1=T3=90° C., and T2=T4=40 to 45° C.).
 13. The adsorption heatpump as claimed in claim 12, wherein T0 is 10° C. and T2 is 40° C. 14.The adsorption heat pump as claimed in claim 12, wherein T0 is 5° C. andT2 is 40° C.
 15. The adsorption heat pump as claimed in claim 12,wherein T0 is 10° C. and T2 is 45° C.
 16. The adsorption heat pump asclaimed in any one of claims 12 to 15, characterized in that theadsorbent has a region in which the adsorption amount difference is 0.15g/g or larger in the range in which φ1 b and φ2 b are from 0.115 to 0.18and φ1 b is equal to or higher than φ2 b.
 17. The adsorption heat pumpas claimed in any one of claims 12 to 16, characterized in that thezeolite comprises a heteroatom in the framework structure.
 18. Theadsorption heat pump as claimed in claim 17, characterized in that theproportions of aluminum, phosphorus, and the heteroatom present in thezeolite are as follows: 0.001≦x≦0.3 (x=molar proportion of theheteroatom in the framework structure to the sum of aluminum,phosphorus, and the heteroatom in the framework structure); 0.3≦y≦0.6(y=molar proportion of aluminum in the framework structure to the sum ofaluminum, phosphorus, and the heteroatom in the framework structure);0.3≦z≦0.6 (z=molar proportion of phosphorus in the framework structureto the sum of aluminum, phosphorus, and the heteroatom in the frameworkstructure).
 19. The adsorption heat pump as claimed in any one of claims12 to 18, characterized in that the zeolite is a zeolite having aframework density of from 10.0 T/1,000 Å³ to 16.0 T/1,000 Å³.
 20. Anadsorption heat pump which comprises an adsorbate, anadsorption/desorption part having an adsorbent for adsorbateadsorption/desorption, a vaporization part for adsorbate vaporizationwhich has been connected to the adsorption/desorption part, and acondensation part for adsorbate condensation which has been connected tothe adsorption/desorption part, characterized in that the adsorbentcomprises a zeolite containing aluminum, phosphorus, and a heteroatom inthe framework structure.
 21. An adsorption heat pump which comprises (a)an adsorbate, (b) an adsorption/desorption part having an adsorbent foradsorbate adsorption/desorption, (c) a vaporization part for adsorbatevaporization which has been connected to the adsorption/desorption part,and (d) a condensation part for adsorbate condensation which has beenconnected to the adsorption/desorption part, characterized in that theadsorbent comprises a zeolite containing aluminum, phosphorus, andsilicon in the framework structure, and that the zeolite gives a²⁹Si-NMR spectrum in which the integrated intensity area for the signalsat from −108 ppm to −123 ppm is not more than 10% based on theintegrated intensity area for the signals at from −70 ppm to −123 ppm.22. Use of an adsorbent as an adsorbent for an adsorption heat pump, theadsorbent being one which, when examined at 25° C., gives a water vaporadsorption isotherm which, in the relative vapor pressure range of from0.05 to 0.30, has a relative vapor pressure region in which a change inrelative vapor pressure of 0.15 results in a change in water adsorptionamount of 0.18 g/g or larger.
 23. The use of an adsorbent as anadsorbent for an adsorption heat pump as claimed in claim 22, whereinthe adsorbent comprises a zeolite having a framework density in therange of from 10.0 T/1,000 Å³ to 16.0 T/1,000 Å³.
 24. The use as claimedin claim 23, wherein the adsorbent is an adsorbent having a porediameter of from 3 Å to 10 Å and a heat of adsorption of from 40 kJ/molto 65 kJ/mol.
 25. The use as claimed in any one of claims 22 to 24,characterized in that the adsorbent is a zeolite containing aluminum,phosphorus, and a heteroatom in the framework structure.
 26. The use asclaimed in claim 25, wherein the zeolite is one in which the proportionsof atoms present therein are represented by the following expressions(1), (2), and (3): 0.001≦x≦0.3  (1) (wherein x represents the molarproportion of the heteroatom in the framework structure to the sum ofaluminum, phosphorus, and the heteroatom in the framework structure);0.3≦y≦0.6  (2) (wherein y represents the molar proportion of aluminum inthe framework structure to the sum of aluminum, phosphorus, and theheteroatom in the framework structure); 0.3≦z≦0.6  (3) (wherein zrepresents the molar proportion of phosphorus in the framework structureto the sum of aluminum, phosphorus, and the heteroatom in the frameworkstructure).
 27. The use as claimed in claim 25 or 26, wherein theheteroatom is silicon.
 28. The use as claimed in claim 25 or 26, whereinthe heteroatom is silicon and the zeolite gives a ²⁹Si-MAS-NMR spectrumin which the integrated intensity area for the signals at from −108 ppmto −123 ppm is not more than 10% based on the integrated intensity areafor the signals at from −70 ppm to −123 ppm.
 29. The use as claimed inclaim 28, wherein the zeolite gives a ²⁹Si-MAS-NMR spectrum in which theintegrated intensity area for the signals at from −70 ppm to −92 ppm isnot less than 25% based on the integrated intensity area for the signalsat from −70 ppm to −123 ppm.
 30. The use as claimed in any one of claims23 to 29, wherein the zeolite is one having the structure represented byCHA in terms of the code defined by International Zeolite Association(IZA).
 31. The use as claimed in any one of claims 23 to 30, wherein theadsorbent has a zeolite content of 60% by weight or higher based on thewhole adsorbent.
 32. The use as claimed in any one of claims 22 to 31,wherein the adsorbent, when examined at 25° C., gives a water vaporadsorption isotherm in which the adsorption amount at a relative vaporpressure of 0.05 is 0.15 g/g or less.
 33. Use of a water vapor adsorbentas an adsorbent for an adsorption heat pump, the adsorbent (1)comprising a zeolite containing aluminum and phosphorus in the frameworkstructure and (2) having a region in which the adsorption amountdifference as determined with the following equation is 0.15 g/g orlarger in the range in which the relative vapor pressure φ2 duringadsorption operation in an adsorption/desorption part is from 0.115 to0.18 and the relative vapor pressure φ1 during desorption operation inthe adsorption/desorption part is from 0.1 to 0.14: Adsorption amountdifference=Q 2−Q 1 wherein Q1=adsorption amount at φ1 as determined froma water vapor desorption isotherm obtained at a temperature (T3) usedfor desorption operation in the adsorption/desorption part Q2=adsorptionamount at φ2 as determined from a water vapor desorption isothermobtained at a temperature (T4) used for desorption operation in theadsorption/desorption part, provided that φ1 (relative vapor pressureduring desorption operaton in the adsorption/desorptionpart)=[equilibrium water vapor pressure at the temperature of coolant(T2) cooling the condenser]/[equilibrium water vapor pressure at thetemperature of heat medium (T1) heating the adsorption/desorption part]φ2 (relative vapor pressure during adsorption operation in theadsorption/desorption part)=[equilibrium vapor pressure at thetemperature of cold (T0) generated in a vaporization part]/[equilibriumvapor pressure at the temperature of coolant (T2) cooling theadsorption/desorption part] (wherein T0=5 to 10° C., T1=T3=90° C., andT2=T4=40 to 45° C.).
 34. The use as claimed in claim 33, wherein T0 is10° C. and T2 is 40° C.
 35. The use as claimed in claim 33, wherein T0is 5° C. and T2 is 40° C.
 36. The use as claimed in claim 33, wherein T0is 10° C. and T2 is 45° C.
 37. The adsorption heat pump as claimed inany one of claims 33 to 36, characterized in that the adsorbent has aregion in which the adsorption amount difference is 0.15 g/g or largerin the range in which φ1 and φ2 are from 0.115 to 0.18 and φ1 is equalto or higher than φ2.
 38. The use as claimed in any one of claims 33 to37, characterized in that the zeolite contains a heteroatom in theframework structure.
 39. The use as claimed in claim 38, characterizedin that the proportions of aluminum, phosphorus, and the heteroatompresent in the zeolite are as follows: 0.001≦x≦0.3  (1) (x=molarproportion of the heteroatom in the framework structure to the sum ofaluminum, phosphorus, and the heteroatom in the framework structure);0.3≦y≦0.6  (2) (y=molar proportion of aluminum in the frameworkstructure to the sum of aluminum, phosphorus, and the heteroatom in theframework structure); 0.3≦z≦0.6  (3) (z=molar proportion of phosphorusin the framework structure to the sum of aluminum, phosphorus, and theheteroatom in the framework structure).
 40. The use as claimed in claim38 or 39, characterized in that the zeolite is a zeolite having aframework density of from 10.0 T/1,000 Å³ to 16.0 T/1,000 Å³.
 41. An airconditioning system for vehicles which employs the adsorption heat pumpas claimed in any one of claims 1 to 21.